EP0028756B1 - Process for dyeing polyamide fibres - Google Patents
Process for dyeing polyamide fibres Download PDFInfo
- Publication number
- EP0028756B1 EP0028756B1 EP80106575A EP80106575A EP0028756B1 EP 0028756 B1 EP0028756 B1 EP 0028756B1 EP 80106575 A EP80106575 A EP 80106575A EP 80106575 A EP80106575 A EP 80106575A EP 0028756 B1 EP0028756 B1 EP 0028756B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- parts
- dyeing
- compounds
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/06—Material containing basic nitrogen containing amide groups using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
- D06P1/621—Compounds without nitrogen
- D06P1/622—Sulfonic acids or their salts
- D06P1/625—Aromatic
Definitions
- the alkyl radical R may be, for example, the tert-butyl, octyl, nonyl or dodecyl radical, and the alkoxy radicals may be the methoxy, ethoxy, propoxy, isopropoxy, butoxy or hexyloxy radical.
- Suitable hydroxyalkoxy radicals are, for example, the 2-hydroxyethoxy radical, 2-hydroxytopoxy radical, 2-hydroxybutoxy radical or 2-hydroxydecyloxy radical.
- the radical R can be in the o-, m- or p-position to the phenolic hydroxyl group.
- Compounds to be used preferably contain it in the p-position.
- the methylene group is then connected to the benzene ring in the o, o 'position.
- alkyl radicals R 1 which may be mentioned are the methyl, ethyl, propyl or isopropyl radical.
- alkaline earth metal ions such as magnesium or calcium, or preferably monovalent cations, such as the ions of the alkali metals lithium, sodium or potassium, the ammonium ion or substituted ammonium ions, such as the ethylammonium ion, butalammonium ion, cyclohexylammonium ion, hydroxyethyl ethylhydroxyammonium ion, bammethylammonium ion, bammethylammonium ion, bammethylammonium ion, bammethylammonium ion, trihydroxyammonium ion, bmethylethylammonium ion, trihydroxyammonium ion, trihydroxyammonium ammonium ion, trihydroxyammonium ion, trihydroxyammonium ammonium ion, ammonium ammonium ion, trihydro , Bishydroxypropylammoniumion or
- the compound of the formula I can be prepared in a manner known per se by reacting the corresponding phenols with formaldehyde or lower aldehydes such as isobutyraldehyde in the presence of acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride.
- acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride.
- the molecular weight of the condensation products obtained or the degree of polymerization n is essentially determined by the molar ratio of phenolic compound to aldehyde.
- the production of the condensation products is described, for example, in DE-A No. 2306104.
- the sulfonation is carried out in a known manner using, for example, oleum, sulfur trioxide or chlorosulfonic acid, if appropriate in inert solvents. The sulfonation is e.g. described in DE-A No. 1090966.
- Preferred compounds for the dyeing process according to the invention are those compounds of the formula I or their salts in which R represents an alkyl radical containing 4 to 12, in particular 8 or 9, carbon atoms or the cyclohexyl radical, R 1 represents hydrogen, n is a number from 2 to 5 means, and m represents 2 to 5.
- the compounds are preferably used in the form of their lithium, sodium, potassium, ammonium or ammonium salts substituted by hydroxyethyl or hydroxypropyl groups.
- the dyeing of the polyamide materials with metal complex dye and / or acid dyes in the presence of the compounds I can be carried out in such a way that the material to be dyed is introduced into an aqueous liquor heated to 40 to 50 ° C. which contains the metal complex dyes and / or acid dyes, the compounds to be used according to the invention Formula 1 and acids, e.g. Acetic acid, then gradually increases the temperature of the dyebath to 100 to 130 ° C and keeps it at this temperature until it is exhausted. It has proven to be particularly advantageous to pretreat the material to be dyed with an aqueous liquor containing only the compounds and acids containing sulfonic acid groups for a short time at 40 to 50 ° C. and only then to add the dyes to the liquor at temperatures between 40 and 98 ° C. then gradually increase the temperature of the dyebath to 100 to 130 ° C and keep it at this temperature until exhaustion.
- an aqueous liquor heated to 40 to 50 ° C. which contains the metal complex dyes and
- the amounts in which the compounds of the formula are added to the dyeing baths can vary within wide limits; they can easily be determined by preliminary tests. In general, depending on the desired depth of color, amounts of 0.5 to 3 percent by weight, based on the weight of the material to be dyed, have proven successful.
- the dyeing process is suitable for natural polyamides, such as wool and silk, and in particular for dyeing synthetic polyamides, such as polycaprolactam, polyhexamethylene diamine adipate or poly- ⁇ -aminoundecanoic acid with 1: 2 metal complex dyes.
- synthetic polyamides such as polycaprolactam, polyhexamethylene diamine adipate or poly- ⁇ -aminoundecanoic acid with 1: 2 metal complex dyes.
- Suitable dyes are described for example in " Color Index", 3rd edition (1971), Vol. 1.
- polyamide fiber materials in a wide variety of processing forms, for example as a flake, sliver, textured threads, spinning to dye cables, yarn, woven, knitted or non-woven fabrics with metal complex dyes and / or acid dyes in an excellent uniform manner; in particular, the streaky dyeing which occurs easily when dyeing fabrics or knitted fabrics made of synthetic polyamides is avoided.
- a polyamide knitted fabric made of filament threads is introduced in a liquor ratio of 1:15 into a bath heated to 40 ° C. and adjusted to pH 8 with a mixture of monosodium hydrogenphosphate and tetrasodium pyrophosphate, which bath contains 0.24 g / l of the compound described below.
- the material is treated with heating of the bath to 98-115 ° C and then 0.4 g / l of the chromium (1: 2) complex to.
- the dyeing can be carried out with the same success if, instead of the condensation product mentioned, a mixture of 225 parts p-tert-butylphenol, 32 parts 36.5% formaldehyde, g conc. Sulfuric acid (molecular weight 500), 114 parts of chlorosulfonic acid and 86 parts of 25% aqueous ammonia-produced condensation product is used.
- a knitted fabric made of ⁇ -polycaprolactam is introduced in a liquor ratio 1:40 into a bath heated to 50 ° C. and adjusted to pH 8 with trisodium phosphate, which contains 0.3 g / l of the condensation product described below.
- the material is treated while the bath is heated to 98 ° C. and then 0.125 g / l of the chromium (1: 2) complex is set to. After dyeing at 98 ° C. for about 90 minutes, the liquor is exhausted. A light gray coloration of excellent uniformity is obtained.
- the condensation product used is in the manner given in Example 1 from 330 parts of nonylphenol, 94 parts of 37% formaldehyde solution, 1 part of conc. Sulfuric acid (molecular weight 1150), 330 parts of cyclohexane and 166.5 parts of chlorosulfonic acid. Instead of the sodium hydroxide solution, 200 parts of triethanolamine were used for neutralization.
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben von Polyamidfasermaterialien mit Säurefarbstoffen und Metallkomplexfarbstoffen, dadurch gekennzeichnet, dass man die Färbung in Gegenwart von Verbindungen der allgemeinen Formel
- R für einen C4 bis C12-Alkyl-, C1 bis C12-Alk- oxy-, Phenyl-, Cyclohexyl- oder C2 bis C10-Hy- droxyalkoxyrest,
- R, für Wasserstoff oder einen C1 bis C4-Alkylrest,
- n für ganze Zahlen von 1 bis 10, und
- m für Zahlen von 1 bis n + 1 stehen.
- R is a C 4 to C 12 alkyl, C 1 to C 12 alkoxy, phenyl, cyclohexyl or C 2 to C 10 hydroxyalkoxy radical,
- R, represents hydrogen or a C 1 to C 4 alkyl radical,
- n for integers from 1 to 10, and
- m stand for numbers from 1 to n + 1.
Als Alkylrest R seien beispielsweise der tert.-Butyl-, Octyl-, Nonyl- oder Dodecylrest, als Alkoxyreste der Methoxy-, Äthoxy-, Propoxy-, lsopropoxy-, Butoxy- oder Hexyloxyrest genannt. Geeignete Hydroxyalkoxyreste sind beispielsweise der 2-Hydroxyäthoxyrest, 2-Hydroxyptopoxyrest, 2-Hydroxybutoxyrest oder 2-Hydroxydecyloxyrest.The alkyl radical R may be, for example, the tert-butyl, octyl, nonyl or dodecyl radical, and the alkoxy radicals may be the methoxy, ethoxy, propoxy, isopropoxy, butoxy or hexyloxy radical. Suitable hydroxyalkoxy radicals are, for example, the 2-hydroxyethoxy radical, 2-hydroxytopoxy radical, 2-hydroxybutoxy radical or 2-hydroxydecyloxy radical.
Der Rest R kann in o-, m- oder p-Stellung zur phenolischen Hydroxylgruppe stehen. Bevorzugt zu verwendende Verbindungen enthalten ihn in p-Stellung. Die Methylengruppe ist dann in o-, o'-Stellung mit dem Benzolring verbunden.The radical R can be in the o-, m- or p-position to the phenolic hydroxyl group. Compounds to be used preferably contain it in the p-position. The methylene group is then connected to the benzene ring in the o, o 'position.
Als Alkylreste R1 seien beispielsweise der Methyl-, Äthyl-, Propyl- oder Isopropylrest genannt.Examples of alkyl radicals R 1 which may be mentioned are the methyl, ethyl, propyl or isopropyl radical.
Als salzbildende Kationen für die Sulfonsäuren der Formel können Erdalkalimetallionen, wie Magnesium oder Calcium oder vorzugsweise einwertige Kationen, wie die Ionen der Alkalimetalle Lithium, Natrium oder Kalium, das Ammoniumion oder substituierte Ammoniumionen, wie das Äthylammoniumion, Butalammoniumion, Cyclohexylammoniumion, Hydroxyäthylammoniumion, Bishydroxyäthylammoniumion, Trishydroxyäthylammoniumion, Bishydroxypropylammoniumion oder auch quaternäre Ammoniumionen, wie das Bishydroxyäthyldimethylammoniumion oder das Trimethylcyclohexylammoniumion, verwendet werden.As salt-forming cations for the sulfonic acids of the formula, alkaline earth metal ions, such as magnesium or calcium, or preferably monovalent cations, such as the ions of the alkali metals lithium, sodium or potassium, the ammonium ion or substituted ammonium ions, such as the ethylammonium ion, butalammonium ion, cyclohexylammonium ion, hydroxyethyl ethylhydroxyammonium ion, bammethylammonium ion, bammethylammonium ion, bammethylammonium ion, trihydroxyammonium ion, bmethylethylammonium ion, trihydroxyammonium ion, trihydroxyammonium ammonium ion, trihydroxyammonium ion, trihydroxyammonium ammonium ion, ammonium ammonium ion, trihydro , Bishydroxypropylammoniumion or quaternary ammonium ions, such as the Bishydroxyäthyldimethylammoniumion or the Trimethylcyclohexylammoniumion, can be used.
Die Herstellung der Verbindung der Formel I kann in an sich bekannter Weise durch Umsetzung der entsprechenden Phenole mit Formaldehyd oder niederen Aldehyden wie Isobutyraldehyd in Gegenwart von sauren Katalysatoren, wie Schwefelsäure, Toluolsulfonsäure oder Borfluorid erfolgen. Das Molgewicht der erhaltenen Kondensationsprodukte bzw. der Polymerisationsgrad n wird im wesentlichen durch das Molverhältnis von phenolischer Verbindung zu Aldehyd bestimmt. Die Herstellung der Kondensationsprodukte wird beispielsweise in der DE-A Nr. 2306104 beschrieben. Die Sulfonierung wird in bekannter Weise unter Verwendung von beispielsweise Oleum, Schwefeltrioxid oder Chlorsulfonsäure gegebenenfalls in inerten Lösungsmitteln durchgeführt. Die Sulfonierung wird z.B. in der DE-A Nr. 1090966 beschrieben.The compound of the formula I can be prepared in a manner known per se by reacting the corresponding phenols with formaldehyde or lower aldehydes such as isobutyraldehyde in the presence of acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride. The molecular weight of the condensation products obtained or the degree of polymerization n is essentially determined by the molar ratio of phenolic compound to aldehyde. The production of the condensation products is described, for example, in DE-A No. 2306104. The sulfonation is carried out in a known manner using, for example, oleum, sulfur trioxide or chlorosulfonic acid, if appropriate in inert solvents. The sulfonation is e.g. described in DE-A No. 1090966.
Bevorzugte Verbindungen für das erfindungsgemässe Färbeverfahren sind solche Verbindungen der Formel I oder deren Salze, in denen R für einen 4 bis 12, insbesondere 8 oder 9 Kohlenstoffatome enthaltenden Alkylrest oder für den Cyclohexylrest steht, R1 für Wasserstoff steht, n eine Zahl von 2 bis 5 bedeutet, und m für 2 bis 5 steht. Die Verbindungen werden vorzugsweise in Form ihrer Lithium-, Natrium-, Kalium-, Ammonium-oder durch Hydroxyäthyl- oder Hydroxypropylgruppen substituierter Ammoniumsalze eingesetzt.Preferred compounds for the dyeing process according to the invention are those compounds of the formula I or their salts in which R represents an alkyl radical containing 4 to 12, in particular 8 or 9, carbon atoms or the cyclohexyl radical, R 1 represents hydrogen, n is a number from 2 to 5 means, and m represents 2 to 5. The compounds are preferably used in the form of their lithium, sodium, potassium, ammonium or ammonium salts substituted by hydroxyethyl or hydroxypropyl groups.
Das Färben der Polyamidmaterialien mit Metallkomplexfarbstoff und/oder Säurefarbstoffen in Gegenwart der Verbindungen I kann so durchgeführt werden, dass man das Färbegut in eine auf 40 bis 50°C erwärmte wässerige Flotte einbringt, die die Metallkomplexfarbstoffe und/oder Säurefarbstoffe, die erfindungsgemäss zu verwendenden Verbindungen der Formel 1 und Säuren, z.B. Essigsäure, enthält, dann die Temperatur des Färbebades allmählich auf 100 bis 130° C steigert und so lange auf dieser Temperatur hält, bis es erschöpft ist. Als besonders vorteilhaft hat es sich erwiesen, das Färbegut mit einer wässerigen Flotte, die nur die sulfonsäuregruppenhaltige Verbindungen und Säuren enthält, kurze Zeit bei 40 bis 50° C vorzubehandeln und erst dann der Flotte bei Temperaturen zwischen 40 und 98°C die Farbstoffe zuzusetzen, anschliessend die Temperatur des Färbebades allmählich auf 100 bis 130° C zu steigern und bis zur Erschöpfung auf dieser Temperatur zu halten.The dyeing of the polyamide materials with metal complex dye and / or acid dyes in the presence of the compounds I can be carried out in such a way that the material to be dyed is introduced into an aqueous liquor heated to 40 to 50 ° C. which contains the metal complex dyes and / or acid dyes, the compounds to be used according to the invention Formula 1 and acids, e.g. Acetic acid, then gradually increases the temperature of the dyebath to 100 to 130 ° C and keeps it at this temperature until it is exhausted. It has proven to be particularly advantageous to pretreat the material to be dyed with an aqueous liquor containing only the compounds and acids containing sulfonic acid groups for a short time at 40 to 50 ° C. and only then to add the dyes to the liquor at temperatures between 40 and 98 ° C. then gradually increase the temperature of the dyebath to 100 to 130 ° C and keep it at this temperature until exhaustion.
Die Mengen, in denen die Verbindungen der Formel den Färbenädern zugesetzt werden, können in weiten Grenzen schwanken; sie lassen sich durch Vorversuche leicht ermitteln. Im allgemeinen haben sich je nach der gewünschten Farbtiefe Mengen von 0,5 bis 3 Gewichtsprozent, bezogen auf das Gewicht des Färbegutes, bewährt.The amounts in which the compounds of the formula are added to the dyeing baths can vary within wide limits; they can easily be determined by preliminary tests. In general, depending on the desired depth of color, amounts of 0.5 to 3 percent by weight, based on the weight of the material to be dyed, have proven successful.
Das Färbeverfahren eignet sich für natürliche Polyamide, wie Wolle und Seide, und insbesondere zum Färben von synthetischen Polyamiden, wie Polycaprolactam, Polyhexamethylendiaminadipat oder Poly-ω-aminoundecansäure mit 1 :2-Metallkomplexfarbstoffen.The dyeing process is suitable for natural polyamides, such as wool and silk, and in particular for dyeing synthetic polyamides, such as polycaprolactam, polyhexamethylene diamine adipate or poly-ω-aminoundecanoic acid with 1: 2 metal complex dyes.
Geeignete Farbstoffe sind beispielsweise in "Colour Index", 3. Auflage (1971), Bd. 1, beschrieben.Suitable dyes are described for example in " Color Index", 3rd edition (1971), Vol. 1.
Mit Hilfe des erfindungsgmässen Verfahrens gelingt es, Polyamidfasermaterialien in den verschiedensten Verarbeitungsformen, beispielweise als Flocke, Kammzug, texturierte Fäden, Spinnkabel, Garn, Gewebe, Gewirke oder Vlies mit Metallkomplexfarbstoffen und/oder Säurefarbstoffen hervorragend gleichmässig zu färben; insbesondere wird das beim Färben von Geweben oder Gewirken aus synthetischen Polyamiden leicht auftretende Streifigfärben vermieden.With the help of the method according to the invention, it is possible to use polyamide fiber materials in a wide variety of processing forms, for example as a flake, sliver, textured threads, spinning to dye cables, yarn, woven, knitted or non-woven fabrics with metal complex dyes and / or acid dyes in an excellent uniform manner; in particular, the streaky dyeing which occurs easily when dyeing fabrics or knitted fabrics made of synthetic polyamides is avoided.
Die in den nachfolgenden Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the following examples are parts by weight.
Eine Polyamidwirkware aus Filamentfäden wird im Flottenverhältnis 1 :15 in ein auf 40° C erwärmtes und mit einer Mischung aus Mononatriumhydrogenphosphate und Tetranatriumpyrophosphat auf den pH-Wert 8 eingestelltes Bad eingebracht, das 0,24 g/I der nachstehend beschriebenen Verbindung enthält. Man behandelt darin das Material unter Erwärmung des Bades bis auf 98-115° C und setzt dann 0,4 g/I des Chrom-(1:2)-Komplexes von
Nach einer Färbezeit von 60 bis 120 min bei 98° C ist die Flotte erschöpft. Es resultiert eine Bordofärbung mit hoher Egalität. Blaue Färbungen mit hoher Egalität werden erhalten, wenn man den Chromkomplex durch die gleiche Menge des Farbstoffs der DE-B Nr. 1644600, Beispiel 1, der DE-B Nr. 1932647, Beispiel 1A, und der DE-A Nr. 2508506 ersetzt.After a dyeing time of 60 to 120 min at 98 ° C, the liquor is exhausted. The result is a bordo coloring with high levelness. Blue colorations with high levelness are obtained if the chromium complex is replaced by the same amount of the dye of DE-B No. 1644600, Example 1, DE-B No. 1932647, Example 1A, and DE-A No. 2508506.
Die verwendete Verbindung wurde auf folgende Weise hergestellt:
- 1320 Teile Nonylphenol und 1 Teil konz. Schwefelsäure werden bei 90 bis 100°C innerhalb von 1 bis 2 h mit 332 Teilen 36%iger wässeriger Formaldehydlösung versetzt. Es wird 2 h bei 90 bis 100°C nachgerührt und dann das Wasser im Vakuum abdestilliert. Das erhaltene Harz (Molekulargewicht 700) wird in 1000 Teilen Cyclohexan aufgenommen und bei 10 bis 20°C langsam mit 650 Teilen Chlorsulfonsäure versetzt. Man rührt 20 h bei Raumtemperatur und neutralisiert anschliessend unter Zugabe von 650 Teilen 45%iger Natronlauge. Das Cyclohexan und das Wasser werden anschliessend im Rotationsverdampfer abdestilliert. Es werden ca. 2000 Teile eines Hatzes erhalten, das sich nach dem Abkühlen zu einem wasserlöslichen Produkt pulverisieren lässt.
- 1320 parts of nonylphenol and 1 part of conc. 332 parts of 36% aqueous formaldehyde solution are added to sulfuric acid at 90 to 100 ° C. within 1 to 2 h. The mixture is stirred at 90 to 100 ° C for 2 h and then the water is distilled off in vacuo. The resin obtained (molecular weight 700) is taken up in 1000 parts of cyclohexane and slowly mixed with 650 parts of chlorosulfonic acid at 10 to 20 ° C. The mixture is stirred for 20 hours at room temperature and then neutralized with the addition of 650 parts of 45% sodium hydroxide solution. The cyclohexane and the water are then distilled off in a rotary evaporator. Approx. 2000 parts of a batch are obtained, which can be pulverized into a water-soluble product after cooling.
Die in Beispiel 1 beschriebene Färbung wird in gleicher Weise durchgeführt. An Stelle der dort zugesetzten Verbindungen werden jedoch 0,24 Teile des nachfolgend beschriebenen Kondensationsproduktes zugesetzt. Es resultiert ebenfalls eine hervorragend egale Bordofärbung. Das eingesetzte Kondensationsprodukt wurde wie folgt hergestellt:
- 264 Teile p-Cyclohexylphenol und 1 Teil konz. Schwefelsäure werden mit 300 Teilen Xylol vermischt und bei 100 bis 110° C langsam mit 82 Teilen 36,5%igem wässerigen Formaldehyd versetzt. Das Wasser wird gleichzeitig über einen Wasserabscheider abdestilliert. Das Xylol wird im Vakuum abdestilliert, das erhaltene Harz (Molekulargewicht 600) in 500 Teilen Trichloräthylen gelöst und bei 10 bis 20° C mit 130 Teilen Chlorsulfonsäure langsam versetzt. Man rührt 12 h bei Raumtemperatur und 30 min bei 50°C nach und neutralisiert bei 20 bis 40°C mit 130 Teilen 45%iger Natronlauge. Durch Einengen im Vakuum werden ca. 410 Teile eines viskosen Harzes erhalten, das sich nach dem Abkühlen zu einem wasserlöslichen, weissen Produkt pulverisieren lässt.
- 264 parts of p-cyclohexylphenol and 1 part of conc. Sulfuric acid is mixed with 300 parts of xylene and 82 parts of 36.5% aqueous formaldehyde are slowly added at 100 to 110 ° C. The water is distilled off simultaneously via a water separator. The xylene is distilled off in vacuo, the resin obtained (molecular weight 600) is dissolved in 500 parts of trichlorethylene and 130 parts of chlorosulfonic acid are added slowly at 10 to 20 ° C. The mixture is stirred for 12 h at room temperature and 30 min at 50 ° C and neutralized at 20 to 40 ° C with 130 parts of 45% sodium hydroxide solution. By concentrating in vacuo, approx. 410 parts of a viscous resin are obtained, which after cooling can be pulverized into a water-soluble, white product.
Mit gleichem Erfolgt lässt sich die Färbung durchführen, wenn an Stelle des genannten Kondensationsproduktes ein in gleicher Weise aus 225 Teilen p-tert.-Butylphenol, 32 Teile 36,5%igem Formaldehyd, g konz. Schwefelsäure (Molekulargewicht 500), 114 Teilen Chlorursulfonsäure und 86 Teile 25%igem wässerigen Ammoniak hergestelltes Kondensationsprodukt verwendet wird.The dyeing can be carried out with the same success if, instead of the condensation product mentioned, a mixture of 225 parts p-tert-butylphenol, 32 parts 36.5% formaldehyde, g conc. Sulfuric acid (molecular weight 500), 114 parts of chlorosulfonic acid and 86 parts of 25% aqueous ammonia-produced condensation product is used.
Ein Gewirk aus ω-Polycaprolactam wird im Flottenverhältnis 1 :40 in ein auf 50°C erwärmtes und mit Trinatriumphosphat auf pH-Wert 8 eingestelltes Bad eingebracht, das 0,3 g/I des nachfolgend beschriebenen Kondensationsproduktes enthält. Man behandelt darin das Material unter Erwärmung des Bades auf 98° C und setzt dann 0,125 g/I des Chrom-(1 :2)-Komplexes von
Das verwendete Kondensationsprodukte wird in der in Beispiel 1 angegebenen Weise aus 330 Teilen Nonylphenol, 94 Teilen 37%iger Formaldehydlösung, 1 Teil konz. Schwefelsäure (Molekulargewicht 1150), 330Teilen Cyclohexan und 166,5 Teilen Chlorsulfonsäure hergestellt. An Stelle der Natronlauge wurden zur Neutralisation 200 Teile Triäthanolamin verwendet.The condensation product used is in the manner given in Example 1 from 330 parts of nonylphenol, 94 parts of 37% formaldehyde solution, 1 part of conc. Sulfuric acid (molecular weight 1150), 330 parts of cyclohexane and 166.5 parts of chlorosulfonic acid. Instead of the sodium hydroxide solution, 200 parts of triethanolamine were used for neutralization.
Claims (3)
or water-soluble salts thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2945102 | 1979-11-08 | ||
| DE19792945102 DE2945102A1 (en) | 1979-11-08 | 1979-11-08 | METHOD FOR DYING POLYAMIDE FIBERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0028756A2 EP0028756A2 (en) | 1981-05-20 |
| EP0028756A3 EP0028756A3 (en) | 1981-06-03 |
| EP0028756B1 true EP0028756B1 (en) | 1983-07-20 |
Family
ID=6085473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80106575A Expired EP0028756B1 (en) | 1979-11-08 | 1980-10-25 | Process for dyeing polyamide fibres |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4295852A (en) |
| EP (1) | EP0028756B1 (en) |
| JP (1) | JPS5673180A (en) |
| DE (2) | DE2945102A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3368956D1 (en) * | 1982-09-03 | 1987-02-12 | Ciba Geigy Ag | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres |
| DE3442888C2 (en) * | 1983-12-05 | 1993-10-28 | Sandoz Ag | Sulphated, optionally sulphonated, oxyalkylated alkylphenol-formaldehyde condensation products, processes for their preparation and their use as dyeing aids |
| US5470355A (en) * | 1983-12-05 | 1995-11-28 | Sandoz Ltd. | Organic compounds |
| DE3673008D1 (en) * | 1983-12-16 | 1990-08-30 | Monsanto Co | Stain-resistant NYLON CARPETS. |
| US4592940A (en) * | 1983-12-16 | 1986-06-03 | Monsanto Company | Stain-resistant nylon carpets impregnated with condensation product of formaldehyde with mixture of diphenolsulfone and phenolsulfonic acid |
| US4619853A (en) * | 1983-12-21 | 1986-10-28 | Monsanto Company | Easy-clean carpets which are stain resistant and water impervious |
| US4501591A (en) * | 1983-12-27 | 1985-02-26 | Monsanto Company | Process for conveniently providing stain-resistant polyamide carpets |
| US4879180A (en) * | 1986-03-06 | 1989-11-07 | Monsanto Company | Stain-resistant nylon fibers |
| US4839212A (en) * | 1986-03-06 | 1989-06-13 | Monsanto Company | Stain resistant nylon carpets |
| EP0242496B1 (en) * | 1986-03-06 | 1991-12-27 | Monsanto Company | Stain-resistant nylon fibers |
| US4800118A (en) * | 1987-11-04 | 1989-01-24 | West Point Pepperell | Compositions and methods for imparting stain resistance to textile articles |
| JPH02262862A (en) * | 1989-02-22 | 1990-10-25 | Matsushita Electric Ind Co Ltd | Brushless motor |
| JPH02269452A (en) * | 1989-04-07 | 1990-11-02 | Matsushita Electric Ind Co Ltd | Brushless motor |
| AU684991B2 (en) * | 1994-08-08 | 1998-01-08 | Wool Research Organisation Of New Zealand Inc. | A method of preventing photobleaching of wool and/or other natural fibres |
| CN103243582A (en) * | 2013-04-16 | 2013-08-14 | 杜芳莉 | Acidic levelling agent and preparation method thereof |
| CN104532620A (en) * | 2014-12-24 | 2015-04-22 | 常熟市淼泉盛达助剂厂 | Levelling agent for wool and real silk |
| CN104532621A (en) * | 2014-12-24 | 2015-04-22 | 常熟市淼泉盛达助剂厂 | Dispersing and leveling agent for fabrics |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE584642A (en) * | 1958-11-14 | |||
| US3118723A (en) * | 1961-02-08 | 1964-01-21 | Arthur J I Harding | Process for dyeing nylon to produce multi-colored dyeings |
| DE1769613A1 (en) * | 1968-06-15 | 1971-07-01 | Bayer Ag | Agent for improving the wet fastness properties of dyes produced with cationic dyes on synthetic polyamides |
| DE1793299A1 (en) * | 1968-08-28 | 1972-02-17 | Bayer Ag | Sulfonation products |
| BE759823A (en) * | 1969-12-03 | 1971-05-17 | Bayer Ag | AGENTS IMPROVING WET SOLIDITY |
| US3993439A (en) * | 1970-07-03 | 1976-11-23 | Hoechst Aktiengesellschaft | Dispersing and stabilizing agents for dyestuffs |
| BE795961A (en) * | 1972-02-25 | 1973-08-27 | Hoechst Ag | APPLICATION OF SULPHURIC HEMI-ESTERS TO DISPERSION OF COLORANTS |
| FR2398835A1 (en) * | 1977-07-28 | 1979-02-23 | Protex Manuf Prod Chimiq | Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content |
-
1979
- 1979-11-08 DE DE19792945102 patent/DE2945102A1/en not_active Withdrawn
-
1980
- 1980-10-25 DE DE8080106575T patent/DE3064313D1/en not_active Expired
- 1980-10-25 EP EP80106575A patent/EP0028756B1/en not_active Expired
- 1980-11-03 US US06/202,907 patent/US4295852A/en not_active Expired - Lifetime
- 1980-11-06 JP JP15525980A patent/JPS5673180A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0028756A2 (en) | 1981-05-20 |
| US4295852A (en) | 1981-10-20 |
| JPS5673180A (en) | 1981-06-17 |
| JPS61476B2 (en) | 1986-01-08 |
| DE2945102A1 (en) | 1981-05-14 |
| DE3064313D1 (en) | 1983-08-25 |
| EP0028756A3 (en) | 1981-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0028756B1 (en) | Process for dyeing polyamide fibres | |
| DE1793482B2 (en) | New Bls-stilbene compounds and processes for their production | |
| DE620462C (en) | Process for the preparation of dyes of the triarylmethane series | |
| DE1593978C3 (en) | Process for the preparation of sulfones containing sulfonic acid groups | |
| DE1769613A1 (en) | Agent for improving the wet fastness properties of dyes produced with cationic dyes on synthetic polyamides | |
| DE1203727B (en) | Process for improving the fastness properties of dyes produced with acid dyes on polyamide structures | |
| US3257379A (en) | Monoazo beta-resorcylic acid dyes | |
| DE1909966C3 (en) | Fertilize compounds containing sulfonic acid groups | |
| DE1793299A1 (en) | Sulfonation products | |
| DE2116560A1 (en) | Sulfomeric phenol ethers | |
| EP0360735A1 (en) | Process for trichromic dyeing or printing | |
| DE3442888C2 (en) | Sulphated, optionally sulphonated, oxyalkylated alkylphenol-formaldehyde condensation products, processes for their preparation and their use as dyeing aids | |
| CH635856A5 (en) | NEW DISAZO DYES AND THEIR PRODUCTION. | |
| EP0474594B1 (en) | Process for dyeing of wool and mixtures thereof with other fibres with reactive dyestuffs | |
| DE1935004B1 (en) | Process for dyeing and / or printing synthetic polyamides | |
| DE865889C (en) | Process for stripping acidic or substantive dyes from fibers made from synthetic linear high polymers with amide groups in the chain | |
| DE2120387C3 (en) | Process for the production of multi-colored dyed wool-containing acrylic textile products | |
| DE1160126B (en) | Process for the production of water-soluble reactive dyes of the anthraquinone series | |
| DE1519505C (en) | Process for dyeing synthetic polyamides | |
| DE2056009C (en) | Process for uniform and streak-free dyeing of synthetic polyamide fiber material | |
| DE2125098A1 (en) | Alkali-resistant fake dyes | |
| AT230015B (en) | Process for the production of colored viscose rayon threads | |
| DE2345124A1 (en) | Dyeing of polyamides before spinning into fibres - using 1-amino 4(trimethylanilino)anthraquinone 2-sulphonic acid | |
| DE1959051A1 (en) | Dyeing fibrous material with cationic dyes | |
| EP0061025A1 (en) | Process for spin-dyeing linear synthetic polyamides with lithium salts of 1:2 metal-complex dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| 17P | Request for examination filed |
Effective date: 19801025 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT LI |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 3064313 Country of ref document: DE Date of ref document: 19830825 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900922 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900928 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19901012 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19901018 Year of fee payment: 11 |
|
| ITTA | It: last paid annual fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19911025 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19911031 Ref country code: CH Effective date: 19911031 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19920630 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19920701 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |